傳統微波消化法是將酸試劑直接與樣品接觸反應，而使得樣品溶解，而分析前通常必須將酸稀釋到適當濃度，以減輕酸試劑所造成的非光譜干擾性和保護儀器裝置(使用HF時)，加上若使用一般等級的酸試劑，則會使得試劑空白值增加，如此一來對樣品中微量分析物的偵測就變得更加困難。而本研究所利用之酸蒸氣消化法，能在同一實驗步驟中具有酸試劑純化、樣品溶解以及基質移除等優點。由於在分析前能有效移除主要基質，可減輕感應偶合電漿質譜儀(ICP-MS)分析常見之非光譜性干擾。同時因具有酸純化之功能，可使用一般等級的酸進行消化，不必使用價格昂貴的高等級酸試劑即可得到非常低的試劑空白值(ng g-1)，因而偵測極限可在ng g-1或sub ng g-1等級。
本研究內容分為兩部分，第一部分是利用密閉式微波消化系統，於消化瓶中另放置鐵氟龍材質的內杯，杯內放置硒或鍺粉末樣品，消化瓶中放置硝酸與鹽酸的混酸，經微波輔助加熱而使其產生混酸蒸氣與內杯中之樣品主要基質反應產生揮發性氯化硒或氯化鍺，而由內杯移至消化瓶中，以達到基質分離的效果，並配合動態反應管感應偶合電漿質譜儀(DRC-ICP-MS)以偵測高純度的硒、鍺粉末中微量不純物含量。兩種樣品在消化2小時後都可達到98~99%的基質移除率。不純物Mg、Cr、Mn、Fe、Ni、Co、Cu、Zn、Ag、Cd、Ba及Pb等元素的回收率可達91-107%。電漿中所形成及樣品基質成分所造成的多原子離子，如40Ar12C+、35Cl16OH+、40Ar16O+、40Ar74Ge+可能會對52Cr+、56Fe+、114Cd+產生同質量干擾，故本研究使用DRC系統以氨氣為反應氣體，其流速定在0.6 ml min-1而q值定為0.6，來減輕多原子離子所造成的光譜干擾以獲得準確之定量結果，並與高解析ICP-MS的定量結果做一比較。
研究第二部分是利用上述系統，以消化矽或石英樣品，消化瓶內則是放置硝酸與氫氟酸混酸溶液，而產生其混酸蒸氣與內杯中之樣品基質反應產生揮發性氟化矽，而由內杯移至消化瓶中之混酸，以達到基質分離的效果，並配合DRC-ICP-MS以偵測半導體級的矽及石英中微量不純物含量。兩類樣品在消化2小時後都可達到98~99%的基質移除率。而不純物Mg、Cr、Mn、Ni、Co、Cu、Zn、Cd、Ba、Pb等元素的回收率則可達83-116%。而石英樣品之定量結果亦與高解析度ICP-MS比較。

Closed-vessel microwave assisted volatilization of Ge, Se, Si and quartz as their volatile compounds , for the determination of trace impurities in high purity Ge, Se, Si and quartz is reported. The volatilization of Ge is 98.7% using vapors of aqua regia whereas vapors generated from 72:1 ratio of HCl:HNO3 is required to volatilize 99.2% of Se. Using vapor of 10:5 ratio of HF:HNO3 , the volatilization of Si is 98.6%, and the volatilization of quartz is 99.0% with 15:3 ratio of the mixed acids. The recoveries of Mg, Cr, Mn,, Ni, Co, Cu, Zn, Cd, Ba and Pb are in the range 83-116%. Determinations are carried out using inductively coupled plasma mass spectrometer with Dynamic Reaction CellTM (DRC ICP-MS). Isobaric interferences, due to the formation of 40Ar12C+, 35Cl16OH+, 40Ar16O+ and 40Ar74Ge+ on the determination of 52Cr+, 56Fe+ and 114Cd+, have been alleviated using ammonia cell gas in DRC. Matrix volatilization using in situ generated acid vapors in closed containers resulted in sub ng mL-1 experimental blanks. Method detection limits are in the low ng g-1 level. The methods developed have been applied to determine trace impurities in high purity Ge, Se, Si and quartz samples.

目 錄
論文摘要……………………………………………………………Ⅰ
謝誌…………………………………………………………………Ⅲ
目錄…………………………………………………………………Ⅳ
圖表目錄……………………………………………………………Ⅶ

第一章 感應偶合電漿質譜儀簡介………………………………1
壹、前言……………………………………………………………1
貳、感應偶合電漿質譜儀基本原理………………………………2
參、分析功能與限制………………………………………………5
一、光譜性干擾………………………………………………6
二、非光譜性干擾…………………………………………………7
肆、動態反應管(Dynamic Reaction Cell)原理………………10
伍、應用實例………………………………………………………14
一、同位素測量………………………………………………14
二、元素分析…………………………………………………16
陸、結論……………………………………………………………17
柒、參考文獻………………………………………………………18

第二章 微波輔助產生揮發性氯化鍺及氯化硒結合感應偶合電漿質譜儀於高純度鍺及硒粉末樣品中微量不純物分析之應用…………20
壹、前言……………………………………………………………20
貳、實驗部份………………………………………………………23
一、儀器裝置及操作條件…………………………………………23
二、試劑藥品及溶液的配製…………………………………25
三、實驗步驟…………………………………………………28
參、結果與討論……………………………………………………28
一、微波消化器升溫條件的探討…………………………………30
二、混酸試劑的組成對於基質移除的影響………………………30
三、DRC之最適化…………………………………………………31
四、高純度鍺和硒中微量不純物之分析…………………………33
肆、結論……………………………………………………………42
伍、參考文獻………………………………………………………43

第三章 微波輔助產生揮發性氟化矽結合感應偶合電漿質譜儀於矽及石英中微量不純物分析之應用……………………………………45
壹、前言……………………………………………………………45
貳、實驗部份………………………………………………………47
一、儀器裝置及操作條件……………………………………47
二、試劑藥品及溶液的配製…………………………………49
三、實驗步驟………………………………………………………50
參、結果與討論……………………………………………………51
一、DRC之最適化…………………………………………………51
二、微波消化器升溫條件的探討…………………………………53
三、混酸試劑的組成對於基質移除和回收率的影響……………53
四、高純度矽和石英中微量不純物之分析………………………56
肆、結論……………………………………………………………62
伍、參考文獻………………………………………………………63

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